점착제의 물성해석과 응용실례 (제10회)

(1)

Vol.7, No.1, 2006 기술강좌(Technical Lecture)

제 5 장 폴리머알로이의 표면 편석과 점착 물성 제어-1

1)

1.

서 론

,

( , )

.

[ (

-co- ): P(VDF-HFA)]

4 ( 4 22 46)

[1-15] .

T

g

, ,

. P(VDF-HFA)

. 5-1 P(VDF-HFA)

, .

/P(VDF-HFA)

. /P(VDF-HFA)

, ,

.

. /P(VDF-HFA)

Corresponding author: e-mail: [email protected]

이 내용은 加納義久古河電氣工業株( ( )) 및 일본 고분자간행회의 허락에 의해 번역된 것입니다.

.

폴리머알로이의 표면편석

2. .

.

. , ,

, [16].

. X

(XPS)[17] 2 (SIMS)[18]

nm .

[19] (AFM)

(PAS-FTIR) [20].

FTIR [21].

(polymer blend) (poly-

mer alloy) .

. ,

, ,

. 5-2

[22].

XPS .

2.1. XPS ?

란

depth profile

X (XPS) .

XPS .

(h ) X

.

( 10 )

김현중

¹

김대준

²

공역

1서울대학교 농업생명과학대학 산림과학부 환경재료과학전공 바이오복합재료 및 접착과학 연구실

2삼성전기 주 생산기술연구소 생산기술팀( )

년 월 일 접수

(2006 2 25 )

(2)

5-1. /P(VDF-HFA)

( )

P(2EHA-AA-VAc) Tg ; -50^oC, ; 28.3 dyn/cm

, , P2EHA

Tg ; -60^oC, ; 35.1 dyn/cm

, , PBA

Tg ; -54^oC, ; 40.0 dyn/cm

LCST Tc<100^oC

, ,

PEA

Tg ; -20^oC, ; 40.8 dyn/cm

LCST Tc=100^oC

, ,

PMA

Tg ; 15^oC, ; 72.8 dyn/cm

LCST Tc=160^oC

, ,

P(2EHA-AA-VAc) : ( 2- -co- -co- ), P2EHA : ( 2- ), PBA : ( ),

PEA : ( ), PMA : ( ), P(VDF-HFA) : ( -co- ) (Tg : -25^oC, Tm :

130^oC, : 20 dyn/cm)

.

h = E

k

+ E

b

+ (1)

. E

k

E

b

.

. E

b

.

. nm

. .

95%

z .

z = 3 cos (2)

. XPS

. Ashley[23]

. (nm) = (M/ n)E

k

/(136lnE

k

176 21000/E

k

) (3)

M n ,

. E

k

(2), (3) .

에 의한 표면편석의 해석

2.2. XPS

Pan [24,25] (PSt)/

(PVME)

.

; LCST

(154

^o

C) 10

XPS . PSt/

PVME PVME =0

^o

(

70 ) PVME

5-1 . PVME

PVME . PVME

. PSt/PVME

(PSt=36, PVME=29(dyn/cm)) .

Sakellariou[26] ( -co- )(MMAS)/

(PEO)

. PEO PMMA

PSt .

St MMA PEO

. 5-2

PEO/MMAS MMAS

(W

^B2

) MMAS (W

^S2

)

. PSt MMAS

(3)

5-2

System Surface Analysis Ref.

Polystyrene-Poly(ethylene oxide) diblock copolymers XPS 1

Polystyrene-Poly(ethylene oxide) triblock copolymers XPS 2

Polystyrene/Poly(ethylene oxide) blends XPS 3

Polystyrene/Poly(vinyl methyl ether) blends XPS, Contact Angle

ATR-FTIR

4,5 6-8

Bisphenol A Polycarbonate/Poly(dimethyl siloxane) blends XPS, ISS 9

Bisphenol A Polycarbonate-Poly(dimethyl siloxan) block copolymers XPS, ISS 10,11

Poly(methyl methacrylate)/Poly(vinyl chloride)blends XPS, ATR-FTIR 12

Poly( -caprolactone)/Poly(vinyl chloride) blends XPS, ATR-FTIR 13,14

Deuterated Polystyrene/Protonated Polystyrene blends FRES 15

Protonated Polystyrene/Perfluorohexane XPS, SIMS 16

End-Capped Deuterated Polystyrene blends XPS, SIMS 16

Amine-Terminated Poly(dimethyl siloxane) XPS 17

Polystyrene-Poly(1,1-dihydroperfluorooctylacrylated)block copolymers XPS 18

Poly( -methylstyrene)-Poly(dimethyl siloxane)block copolymers XPS, TEM 19

Polystyrene-Poly(dimethyl siloxane)block copolymers XPS 20,21

Poly(dimethyl siloxane)/Poly(dimethyl siloxane)-Polystyrene block copolymer blends XPS 22 Poly(dimethyl siloxane)/Poly(dimethyl siloxane)-Poly( -methylstyrene) block copolymer blends XPS 22 Poly(dimethyl siloxane)/Poly(dimethyl siloxane)-Bisphenol A Polycarbonate block copolymer blends XPS 22

Poly(ethylene-co-vinyl acetate)/Tackifier Resins/Wax blends XPS 23

Polystyrene-Poly(methyl methacrylate) block copolymers XPS 24,25

Polysulfone/Polysulfone-Polysiloxane block copolymer blends XPS 26

Poly(vinyl chloride)/Poly(methyl methacrylate)-Poly(dimethyl siloxane) graft copolymer blends XPS 27 Hydroxyethyl methacrylategrafted onto silicone elastomer-Polystyrene block copolymers XPS 28

Poly(butylene terephthalate)-Poly(tetramethylene oxide) block copolymers XPS 29

Poly(methyl methacrylate)/Poly(vinylidene fluoride) blends SIMS 30

Poly( -methylstyrene)-Poly(2-hydroxyethyl methacrylate) block copolymers XPS, Contact Angle 31

Poly(vinyl chloride)/Siloxane-Urethane-Ethyleneoxide oligomer blends XPS 32

Nylon-6/Poly(cis-1,4-butadiene) blends XPS 33

Poly(dimethyl siloxane)-Polyamide block copolymers XPS 34

Polystyrene-Poly(metoxy poly(ethylene glycol)methacrylate) block copolymers XPS 35

Amino-terminated Poly(dimethyl siloxane)/Epoxy Resin blends XPS 36

Poly(methyl methacrylate)/Poly(vinyl acetate) blends XPS 37

Epoxy resin/Poly(methyl methacrylate)-Poly(glycidyl methacrylate)-Poly(dimethyl siloxane methacrylate) block copolymer blends

XPS 38

Poly(dimethyl siloxane)-Nylon-6 diblock copolymers XPS 39

Fluorinated Poly(amide urethane) block copolymers XPS 40

Poly(styrene-co-methyl methacrylate)/Poly(ethylene oxide)blends XPS 41

Deuterated Polystyrene-Polyisoprene diblock copolymer with fluorinated side chain FRES 42

Poly(ethylenepropylene)/Poly(ethyle) SIMS 43

Poly(ethylene-co-(1-dodecane))/Poly(ethylene) SIMS 43

XPS: X-ray photoelectron spectroscopy

ATR-FTIR : Attenuated total reflection fourier transform infrared spectroscopy ISS : Ion scattering spectroscopy

FRES : Forward recoil spectrometry SIMS : Secondary ion mass spectroscopy Ref : 22

(4)

5-1. PSt/PVME

PVME

[24] ) , ) .

5-2. 20%MMA(

, ), 80%MMA( , )

MMAS PEO 69

[26] ( , ) : , ( , ) : .

MMAS

. ,

. PEO/MMAS

(20% MMA) depth profile 5-3

. depth profile

MMAS

5-3.

( ), ( ) PEO/MMAS(60/

40) depth profile [26].

MMAS .

Gardella [27] (PMMA)/

(PVC) XPS

. PMMA/PVC THF

, MEK

. PMMA=

41.2(dyn/cm), PVC=42.0(dyn/cm) ,

. 5-4

XPS PMMA

.

100 . PMMA

. PSt/PVME

.

. Chen [28] A

(BPAC)- (PDMS)

XPS

. PDMS

. [29]

.

블렌드의 표면편석

3. PEA/P(VDF-HFA)

LCST T

c

Shift

.

(5)

5-4. PMMA/PVC

(A) THF , (B) MEK [27)].

5-5.

/P(VDF-HFA)

LCST .

5-5 .

PEA , PBA

P2EHA 2-

.

. PEA/P(VDF-HFA)

5-6. PEA/P(VDF-HFA)

[12]

(Td; ) .

Flory-Huggins

, (Tm ; ) DSC .

.

블렌드의 상용성과 표면편석

3.1. PEA/P(VDF-HFA)

5-6 PEA/P(VDF-HFA)

LCST ( T

c

=150

^o

C)

T

d

(T

m

=

110 130

^o

C) [12].

T

g

T

m

.

(T

g

T

m

(6)

5-7.

15^o PEA/P(VDF-HFA) [14] )

, ) .

.

15

^o

XPS PEA/P(VDF-

HFA)

5-7 [14]. 140

^o

C 1

. PEA/P

(VDF-HFA) .

P(VDF-HFA)

P(VDF-HFA) PEA

. P(VDF-HFA)

. PEA/P(VDF-HFA) T

m

. T

m

.

5-8 140

^o

C

15

^o

( 2 nm)

P(VDF-HFA)

[13]. 90

^o

( 6 8 nm)

P(VDF-HFA)

. 6 8 nm PEA/P

(VDF-HFA)

. P(2EHA-AA-VAc)/P(VDF-HFA)

5-8. PEA/P(VDF-HFA)

[ ; ) 15^o, ) 90^o.

6 8 nm .

. PEA/P(VDF-HFA)

depth profile .

3.2. PEA/P(VDF-HFA)

블렌드에 있어서 표면편석의 시뮬 레이션

Kammer[30]

. PSt/PVME

.

. PEA/P(VDF-HFA)

. 3.2.1. Kammer

.

i

dµ

i

= 0, Ad = -

iS

dµ

i

(4)

A , , µ

i

iS

(7)

5-9.

P(VDF-HFA) ,

15^o XPS .

(k=10^-40, X=

200), [13]

.

Ad = = (

i

-

iS

)dµ

i

(5)

.

dµ

i

= G

ik

d

k

(6)

G

ik i k

Gibbs

. (5) (6)

(7) .

Ad = (

i

-

iS

)G

ik

d

i

(7)

2 (7)

.

Ad = ( i - i

^S

)G

H

d

i

(8)

Kammer

S

Langmuir-type .

S

= k / [ 1 + (k-1) ] (9)

k . G

H

2 Flory-Huggin [31].

G

H

/ RT = 1/[r

1

] + 1/[r

2

(1- )] - 2X (10)

X [31] PVT

. r

i

. (8), (9) (10) .

A( -

2

)/RT = Bln[1-(1-k) ] +

(1/r

1

- 1/r

2

) - X [2k/(1-k)+ ] (11) B = -(r

1

-r

2

k)/[r

1

r

2

(1-k)] - 2Xk/(1-k)

²

(12)

.

=

1

+

2

(1- ) + (13)

Kammer

.

A / RT =

B[ln{1-(1-k) } - lnk] + X (1- ) (14)

3.2.2. Kammer

X, k (11) (14) .

PEA/P(VDF-HFA) . PEA/P

(VDF-HFA) 140

^o

C PVT

P(VDF-HFA)

.

= -17.29(

1

) + 35.96 (15)

1

P(VDF-HFA)

.

1

PVT

.

15

^o

XPS (15)

P(VDF-HFA)

5-9 [13]. Kammer

k=10

^-40

, X=200 .

vs.

1

. k

Kammer

(8)

5-10.

15^o P(VDF-HFA)

P(VDF-HFA) .

[13]

15

^o

P(VDF-HFA) P(VDF-HFA)

[13].

. PEA/P(VDF-HFA)

. 2

Kammer

.

X, k .

3.2.3. PEA/P(VDF-HFA) Depth Profile depth

profile [32-

36]. PEA/P(VDF-HFA) depth profile Schmidt Binder

[34] . depth profile

b

[36]

.

1

(d) =

1b

+ (

1S

-

1b

)exp(-d /

b

) (16)

b, S ,

1

(d)

d .

b

.

b

= ( /6)

1b

(1-

1b

)(X-XS)

^-0.5

(17)

X , X

S

5-11. XPS

PEA/P(VDF-

HFA) depth profile (ln( 1(d)- 1b

) vs.

(d) )[14] P(VDF-HFA) (wt%) : a) 30, b) 70.

.

X

S

= 0.5{(N

1 1

)

^-1

+ [N

2

(1-

1

)]

^-1

] (18)

N . Kuhn

2 <R

gyr2

>

^0.5

.

1

=

2

= = <R

gyr2

>

^0.5

(6/N)

^0.5

(19)

= (

12

1

+

22

2

)

^0.5

(20)

2 depth profile X, X

S

,

.

(16) .

ln[

1

(d)-

1b

] = (-1/

^b

) d + ln(

1S

-

1b

) (21)

(9)

ln[

1

(d)-

1b

] vs. d

^b

. PEA/P(VDF-HFA) depth profile ln[

1

(d)-

1b

] vs. d

^b

.

5-11 XPS PEA/P

(VDF-HFA) (70/30), (30/70) depth profile (ln [

1

(d)-

1b

] vs. d ) [14]. ln[

1

(d)-

1b

] vs. d

b

. PEA/P(VDF-HFA)

Schmidt Binder .

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